Oxonol dyes and process for preparing oxonol dyes

ABSTRACT

Oxonol dyes represented by the formula:   WHERE R1 and R2 and n are as defined in the specification. A condensation process for preparing the same is also described.

- States Patent [191 ltohayashi et al.

I OXONOL DYES AND PROCESS FOR PREPARING OXONOL DYES 211 Appl. No.: 356,226

[30] Foreign Application Priority Data May 2, 1972 Japan 46-43868 [52] U.S. CI. 260/240.2, 96/84 R, 260/290 I-IL, 260/290 R, 260/294.9, 260/310 A, 260/566 B [5 1] Int. Cl C09b 23/04 [58] Field of Search 260/240.2

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 43-3504 2/l968 Japan 260/2402 1 Feb. 11,197s

LIT/.429 1/1970 Great Britain 2610/2402 Primary E.\'aminerJohn D. Randolph Attorney, Agent. or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT Oxonol dyes represented by the formula:

i i R2 R2 where R and R and n are as defined in the specification. A condensation process for preparing the same is also described.

11 Claims, N0 Drawings OXONOIL DYES AND PROCESS FOR PREPARING OXONOL DYES BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION According to the present invention, oxonol dyes represented by the following formula (I) are provided:

wherein R, represents an alkyl group, i.e., a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, hydroxyalkyl such as hydroxyethyl, cyanoalkyl such as cyanoethyl, hydroxyalkoxyalkyl such as hydroxyethoxyethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, or benzyl, etc.) or an aryl group, i.e., a substituted or unsubstituted aryl group (e.g., phenyl or naphthyl based materials such as phenyl, alkylaryl, e.g., tolyl, ethylphenyl, halogenoaryl, e.g., chlorophenyl, alkoxyaryl, e.g., methoxyphenyl, or naphthyl, etc.), R represents an alkyl group having a sulfonic acid group or carboxyl group (e.g., sulfomethyl, carboxymethyl, sulfoethyl, carboxyethyl, sulfopropyl, sulfo-2-methylpropyl, sulfo-2,2- dimethylpropyl, sulfobutyl, carboxybutyl, sulfo-4- ethylbutyl or sulfopentyl etc.), n is 0, l or 2, and the methine chain may be substituted by an alkyl group (e.g., methyl, ethyl, hydroxyalkyl, e.g., hydroxymethyl, propyl, t-butyl, etc.) or an aryl group (e.g., phenyletc.).

The scope of R and R is broad. However, so long as the general criteria of alkyl and aryl for R and carboxyl or sulfonic acid substituted for R is met, these moieties can be freely selected, and the substituted forms above are not limited. Considering the ease of availability of starting materials, however, any alkyl moiety in R,, be it unsubstituted or substituted, preferably has l-l 8 carbon atoms. This is a commercial rather than technical limitation, however. Further, though non-limitative, the R alkyl groups with 1-6 carbon atoms are preferred. In R one carboxyl or sulfonic acid group positioned on a terminal carbon atom is sufficient to obtain te effects of the invention.

The oxonol dyes represented by formula (I) can be prepared by condensing pyrazolone derivatives represented by the following formula (II) with compounds represented by the following formulae (Illa), (IIIb), (lllc), (llld) and (Ille) in the presence of a base;

wherein R R and n each have the same meaning as described above, and X represents an anion (e.g., chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, methylsulfate, ethylsulfate and p-toluenesulfonate, etc.). Any monovalent anion which does not interfere with the reaction can be used for X.

In the case that the dyes represented by formula (I) have the above mentioned substituents in the methine chain, the compounds represented by formulae (Illa) (llle), of course, should have corresponding substituents.

DETAILED DESCRIPTION OF THE INVENTION As the base, triethylamine, diethanolamine, pyridine, piperidine and ammonia gas, etc., are preferably used. Inorganic bases such as ammonium carbonate, sodium carbonate, caustic soda, caustic potash may in general be used with success. Organic bases are preferred, however, since they are easily soluble in the reaction mixture. The amount of base used is generally over equimoler of the pyrazolone. Slightly in excess of 1 mol to 3 mols per mol of pyrazolone is preferred. 1.5-2.5 mols per mole of pyrazolone will commonly be used on an industrial scale.

The condensation reaction is advantageously carried out using a solvent which has the capability of dis solving the pyrazolone derivatives represented by the formula (II). As such solvents, alcohols (e.g., methanol, ethanol, isopropanol and butanol, etc.), ethylene glycol monoalkyl ethers (e.g., ethylene glycol monomethyl ether and ethyleneglycol monoethyl ether, etc.), amides (e.g., acetamide, dimethylformamide and dimethylacetamide, etc.), dimethylsulfoxide or miscible mixtures thereof can be used. Polar solvents are preferred. There is not limitation on the boiling point of solvents. In general, since compounds (III) are more soluble than the pyrazolones, the solvents easily dissolve compounds (Ill). About 2 to 10 parts of solvent per part by weight of pyrazolones is preferred on an industrial scale. The amount in theory is merely that needed for dissolution.

The reaction is advantageously carried out at a temperature up to the boiling point of the solvent used. Since pentamethine dyes n is 2 in the formula (I)) are relatively unstable to heat, it is prefered to carry out the reaction to form the pentamethine dyes with cooling. Therefore, a prefered temperature range is from 0C to the boiling point of the solvent used.

It is preferred that two moles of the pyrazolone derivative represented by the general formula (ll) be employed with respect to a compound represented by any one of the general formulae (llla) through (llle), inclusive. Most preferably, in view of the desire to utilize pyrazolone in the reaction as completely as possible, an additional 0.1 to 0.2 mols of the pyrazolone are used in excess of the 2-fold molar minimum ratio which is preferred.

The pressure of reaction and time of reaction are substantially non-critical, and reaction is usually conducted at normal pressure for times sufficient to complete the reaction. Representative reaction times are set out in the specific Examples at a later point in the specification.

The pyrazolone derivatives represented by formula (ll) can be prepared by known processes. For example, the process described in Annalen der Chemie, vol. 294, pages 232 (1896) can be used. For example, 1- sulfopropyl-3-carboethoxy-5-pyrazolone can be produced by heating the monosodium salt of ethyl oxalate and sulfopropylhydrazine in a weakly alkaline aqueous solution. Further the process described in Jikken Yuki Kagaku written by Seitaro Yamaguchi, published by Nankodo Co. 1954), page 812 can be used. For example, 1-sulfopropyl-3-carboethoxy-5-pyrazolone can be prepared by slowly adding hydrazine hydrate to an ethanol solution of ethyl oxalate with stirring at room temperature and heating the resulting l-l-l-3-carboethoxy- -py'razolone together with l,2-oxathiolan-2,2-dioxide at lC in an oil bath with stirring.

The compounds represented by the formulae (llla)-(llle) which are raw materials for forming the methine chain of the dyes represented by the formula (l) can also be prepared by well known processes. Namely, the compounds represented by the formula (llla) can be prepared by the process described in Chemical Abstracts, vol. 28, page 493 (1934), Berichte der Deutschen Chemischen Gesellschaft, vol. 36, page 2667 (I903) or Annalen der Chemie, vol. 330, page 367 (1932). The compounds represented by formulae (lllb) and (lllc) are commercially available. The compounds represented by formula (llld) can be prepared by heating 0.1 mol of 2,4-di-nitrochlorobenzene and 0.1 mol of pyridine in 50 ml of acetone for 2 hours on a water bath. The compounds represented by formula (llle) can be prepared by dissolving 0.1 mol of cyanogen bromide in 100 ml of ether, adding dropwise 0.1 mol of pyridine while cooling, and stirring thereafter at room temperature for two hours.

In the dyes prepared by the process of this invention, the sulfonic acid group or the carboxyl group can be in the form of a salt such as an alkali metal salt (e.g., sodium, potassium) or an ammonium salt. These salts can be easily produced by known processes. For example, the potassium salt can be precipitated by adding a methanol solution of potassium acetate or potassium hydroxide to a dye solution.

The oxonol dyes of the present invention are distinguished from known oxonol dyes because they have a carboxylic acid ester bond at the 3-position of the pyrazolone ring and an alkyl group having a water soluble group at the l-position of the pyrazolone ring.

The oxonol dyes according to the present invention are not only characterized by such a new structure but they are also superior to known dyes because they have excellent properties based on the difference of such structure. Namely, when they are used in a light absorbing layer (e.g., antihalation layer and antiirradiation layer) or a filter layer of a photosensitive material they easily decolorize as compared with known oxonol dyes in which the 3-position of the pyrazolone ring is substituted with a methyl group or carboxyl group, and consequently they have the excellent characteristic that residual color does not remain in the photographic materials. Our dyes are particularly suitable for coloring a decolorizable layer in a photographic material, and are used in this use in a conventional manner.

Further, since the l-position of the pyrazolone ring of the dyes of this invention is substituted by an alkyl grop having a water soluble group, the diffusion rate of the dyes of this invention during photographic processing differs greatly from that of analogous dyes having an aryl group having a water soluble group in the 1- position ofthe pyrazolone ring. Consequently, they are removed quickly and completely from layers of the photographic materials. Accordingly, they have the excellent characteristic that residual color is not generated in the case of rapid treatments where all processing steps are carried out within one minute.

For example, results of comparisons of color fading ability with an aqueous solution of sodium sulfite are shown in the following table, in which gelatin films produced using an oxonol dye of the present invention and known oxonol dyes are used.

tion ratio (21) g In the table, the absorption maximum wave length is determined on samples prepared by mixing 1.0 ml of an aqueous solution of mg of the dye in 50 ml of distilled water and 5.0 ml of a 10% aqueous gelatin solution, applying the mixture to a glass plate of 12 X 16.5 cm and drying. The optical density of the sample at the absorption maximum wave length is then determined. The sample is then dipped in a 5% aqueous solution of sodium sulfite at 20C for 30 seconds with stirring and dried. Then the optical density of the sample at the absorption maximum wave length is again determined. The decolorization ratio is calculated from these optical densities by the following equation.

Decolorization ratio =Optical density before treatment Optical density after treatment/Optical density before treatment X 100 As is clear from the above results, the dyes according to the present invention have a good decolorizing property as compared with the known dyes. Further, the known dyes stain the aqueous solution of sodium sulfite because they have an inferior decolorization property upon reduction by sodium sulfite. On the contrary, the

dyes according to the present invention do not stain at all.

The good decolorization ability of the dyes according to the present invention is kept without being influenced by the kind of carboxylic acid ester group at the 3-position of the pyrazolone ring. The dyes according to the present invention have a sulfonic acid group or a carboxyl group at the alkyl group in the 1-position of the pyrazolone ring. These groups render the dyes water soluble and improve the decolorization ability of the dyes in the aqueous solution containing sodium sulfite. Namely, dyes which do not have a water soluble group such as a sulfonic acid group or a carboxyl group at R of formula (I) have an inferior decoloring property. Therefore, they are clearly distinguished from dyes of the present invention.

The present invention will now be illustrated in greater detail by the following examples.

EXAMPLE 1 Synthesis of the following dye:

A mixture composed of 2.78 g of 1-sulfopropy1-3- ethoxycarbonyl-S-pyrazo1one, 1.96 g of diphenylformamidine, 2.0 g of triethylamine and m1 of N,N-dimethylformamide was refluxed at normal pressure for 30 minutes. Fifty (50) ml ofa hot methanol solution containing 1.5 g of anhydrous potassium acetate was added to the resulting yellow reaction solution. The mixture was refluxed for 5 minutes and ice cooled to precipitate yellow crystals. After filtration and drying, 1.9 g of yellow dye was obtained. An aqueous so1ution (1/100,000 parts by weight, same in all Examples) of this dye had a yellowish orange color and an absorp- EXAMPLE 2 Synthesis of the following dye:

HO-C N (SH CHgCHzSOgH lHzCHzCHzSOaH A mixture of 3.06 g of 1-sulfopropyl-3-butoxycarbonyl-5-pyrazolone, 2.0 g of orthoformic acid ester, 2.0 g of triethylamine and ml of N,N-dimethylacetamide was refluxed at normal pressure for 30 minutes. After cooling the reaction solution with ice, a mixture of 2 ml of hydrochloric acid and 30 ml of methanol was added thereto, by which yellow crystals precipitated. These yellow crystals were separated by filtration and washed with methanol and then with acetone to obtain 2.2 g of yellow dye. An aqueous solutoin of this dye had a yellowish orange color. The absorption maximum wave length of the dye was 477 mu.

7 EXAMPLE 3 Synthesis of the following dye:

(EHzCH CILSOQK HhCHzCHzSOaK A mixture composed of 3.9 g of 1-sulfopropyl-3- decaoxycarbonyl-S-pyrazolone, 1.3 of malondialdehyde dianil hydrochloride, 50 ml of methanol and 2 g of triethylamine was refluxed at normal pressure for 3 hours on a water bath. Then, 50 ml of methanol containing 1.5 g of anhydrous potassium acetate was added thereto. By refluxing for 5 minutes, crystals precipitated. These crystals were separated by filtration, washed with methanol and dried to obtain 2.3 g of a dye. An aqueous solution of this dye had a reddish violet color. The absorption maximum wave length of this dye was 554 mu.

Dyes having a similar reddish-violet color were obtained by using 1-sulfopropy1-3-ethoxycarbony1-5- pyrazolone, 1-sulfobutyl-3-ethoxycarbony1-5- pyrazolone, 1-sulfopropy1-3 -butoxycarbonyl-5 pyrazolone, 1 sulfo-2,2-dimethy1propyl-3- decaoxycarbonyl-5-pyrazo1one or 1-su1fo-4- ethylbutyl-3-ethoxycarbonyl-5-pyrazolone instead of 1=su1fopropy1-3-decaoxycarbonyl-S-pyrazolone used in Example 3, and tetramethoxypropane or ,B-methylmalondialdehyde diani] hydrochloride instead of malondialdehyde dianil hydrochloride.

EXAMPLE 4 Synthesis of the following dye:

(illigCIIzCIIzS OaNtt II2CII2CI'I2S OaNtl.

A mixture composed of 5.02 g of 1-sulfopropyl-3- octadecaoxycarbonyl-S-pyrazolone, 2.0 g of tetramethoxypropane, 50 ml or methanol and 2 g of triethylamine was refluxed at atmospheric pressure for 3 hours on a steam bath. The reaction solution gradually changed from a red color to a dark reddish-vio1et color. Then, 20 ml of an aqueous solution containing 5 g of sodium acetate (311 0) was added thereto. After refluxing or 5 minutes, the aqueous solution was cooled with ice. The precipitated dark violet crystals were separated by filtration, washed with methanol and then with acetone and dried to obtain 5.1 g of dark red crystals. An aqueous solution of this dye had a reddish violet color. The absorption maximum wave length of this dye was 556 EXAMPLE ducing an excess amount of ammonia gas, indicated by Synthesis of the following bubbles forming on the surface of the mixture. the mixt omooolc CH1COOK A mixture composed of 4.28 g of l-carboxymethyl-3- l0 ture was allowed to stand overnight at room temperaethoxycarbonyl-S-pyrazolone, 2.84 g of glutaconture and a brilliant green ammonium salt precipitated. dialdehyde dianil hydrochloride, 30 ml of methanol, 30 This dye was separated by filtering, washed with ethaml of N,N-dimethylformamide and 3.2 g of diethanolnol and then with acetone, and dried. Thus, 4.4 g of the amine was stirred at l0l5C for 4 hours at atmodye was obtained. An aqueous solution of this dye had spheric pressure. The reaction solution gradually a deep blue color. The absorption maximum wave changed to a blue color. By adding 50 ml of methanol length of the dye was 661 mu.

containing 1.12 g of potassium hydroxide, the potassium salt of the dye was precipitated. After stirring at EXAMPLE 7 a room temperature for about minutes, the crystals Synthesis of the following dye:

N 0=0 HO-O N N N HzCHzCHzCHzSOaK HzCHzCHgCHzSOaK were filtered and dried in vacuum. 4.1 g of greenish Ammonia gas was introduced into a mixture of 8.1 g blue crystals were thus obtained. An aqueous solution f 1- ulf butyl-3-deca0xycarbonyl-5-pyraz0lone, 100 of this dye had a deep blue color. The absorption maximl of ethanol and 1.9 g of cyanopyridinium bromide at mum Wave length of this y was 660 M- l020C with stirring, by which the contents dissolved.

Dyes having a nearly deep blue color we e ined After introducing an excess amount of ammonia gas, by using l-sulfobutyl-3-ethoxycarbonyl-5-pyrazolone, indicated by bubbles forming on the surface of the mixl-sulfobutyl-3-methoxycarb0nyl-5-pyrazolone, l ture, the system was stirred for 4 hours. Then, 100 ml sulfopropyl-3- 0Xy ar 0nyl-5py of hot methanol containing 2.5 g of potassium acetate sulfopropyl-3-ethoxycarbonyl-5-pyrazolone, lwas added thereto, by which the potassium salt of the sulfopropyl-3-methoxycarbonyl-5pyrazolone, l-SulfO- dye immediately precipitated. The crystals were sepa- 2',2-dimethylpropyl-3-decaoxycarbonyl-5- rated by filtration, washed with 30 ml of methanol and pyrazolone, 1-sulfo-4-ethylbutyl-3-ethoxycarbonyl-S- then with 100 m1 of acetone, and dried. Thus, 7.0 g of pyrazolone, 1-carboxyethyl-3-meth0Xycarb0nyl-5- the dye was obtained. An aqueous solution of this dye pyrazolone, l-carboxyethyl-3-ethoXy rbonyl-5- had a deep blue color. The absorption maximum wave pyrazolone, l-carboxyethyl-3-butoxycarbonyl-5- length wa 663 mu. pyrazolone, l-carboxymethyl-3-methoxycarbonyl-5- While the invention has been described in detail and pyrazolone, l-carboxymethyl-3-butoxycarb0nyl5- with reference to specific embodiments thereof, it will pyrazolone, l-carboxymethyl-3-decaoxycarbonyl-5- be apparent to one skiled in the art that various pyrazolone or l-carboxymethyl-3-octadecaoxycarbochanges and modifications can be made therein withnyl-S-pyrazolone instead of l-carboxymethyl-3- out departing from the spirit and scope thereof. ethoxycarbonyl-5-pyrazolone used in Example 5, or What is claimed is: 'y-methyl-glutacondialdehyde dianil hydrochloride, 1. An oxonol dye selected from the dyes of the fory-ethyl-glutacondialdehyde dianil hydrochloride, 2',4- mula dinitro-4-methylpyridinium chloride, 2,4-dinitro-4- phenylpyridinium chloride or 2,4'-dinitro-4- ethylpyridinium chloride instead ofglutacondialdehyde (|3:CH(CH=CH)"C"C C00R N o=o HOC N dianil hydrochloride. N \N/ EXAMPLE 6 I l R2 R2 Synthesis of the following dye:

H00400o-oo=oHoH=oHoH;oH%-ficooolflo =0 HO-C N N o N HzCHzCOONHt CHzCHaCOONH Ammonia gas was introduced into a mixture comwherein R represents a C -C alkyl group, a phenyl posed of 4.56 g of l-carboxyethyl-3-butoxycarbonyl-5- group or a naphthyl group, R represents a C -C alkyl pyrazolone, 50 ml of ethanol and 2.8 g of 2,4- group having a sulfonic acid group or carboxyl group,

dinitrobenzene pyridinium chloride with stirring at n is 0, 1 or 2, and the methine chain may be substituted 10-20C, by which the contents dissolved. After introby an alkyl group, a phenyl group or a naphthyl group.

2. An oxonol dye as claimed in claim 1 wherein R is selected from the group consisting of hydroxyalkyl, cyanoalkyl, hydroxyalkoxyalkyl where the alkyl moiety has 1-18 carbon atoms.

3. An oxonol dye as claimed in claim 1 wherein R is benzyl.

4!. An oxonol dye as claimed in claim 1 wherein R is phenyl or naphthyl.

5. An oxonol dye as claimed in claim 4 wherein R is benzyl, halogen or alkoxy substituted phenyl or naphthyl.

6. An oxonol dye as claimed in claim 1 wherein R is methyl, ethyl, hydroxyethyl, cyanoethyl, hydroxyethoxyethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, or benzyl, R is phenyl, tolyl, ethylphen'yl, chlorophenyl, methoxyphenyl, naphthyl, sulfomethyl, carboxymethyl, sulfoethyl. carboxyethyl, sulfopropyl, sulfo-2-methylpropyl, sulfo-2,Z-dimethylpropyl, sulfobutyl, carboxybutyl, sulfo-4-ethylbutyl or sulfopentyl, and the methine chain, if substituted, is substituted with methyl, ethyl; hydroxymethyl, propyl, t-butyl or phenol.

7. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula 8. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula II N 9. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula 10. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula l CHzCHzCHzS 03K 

1. AN OXONOL DYE SELECTED FROM THE DYES OF THE FORMULA
 2. An oxonol dye as claimed in claim 1 wherein R1 is selected from the group consisting of hydroxyalkyl, cyanoalkyl, hydroxyalkoxyalkyl where the alkyl moiety has 1-18 carbon atoms.
 3. An oxonol dye as claimed in claim 1 wherein R1 is benzyl.
 4. An oxonol dye as claimed in claim 1 wherein R1 is phenyl or naphthyl.
 5. An oxonol dye as claimed in claim 4 wherein R1 is benzyl, halogen or alkoxy substituted phenyl or naphthyl.
 6. An oxonol dye as claimed in claim 1 wherein R1 is methyl, ethyl, hydroxyethyl, cyanoethyl, hydroxyethoxyethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, octyl, decyl, dodecyl, pentadecyl, octadecyl, or benzyl, R2 is phenyl, tolyl, ethylphenyl, chlorophenyl, methoxyphenyl, naphthyl, sulfomethyl, carboxymethyl, sulfoethyl, carboxyethyl, sulfopropyl, sulfo-2-methylpropyl, sulfo-2,2-dimethylpropyl, sulfobutyl, carboxybutyl, sulfo-4-ethylbutyl or sulfopentyl, and the methine chain, if substituted, is substituted with methyl, ethyl, hydroxymethyl, prOpyl, t-butyl or phenol.
 7. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula
 8. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula
 9. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula
 10. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula
 11. An oxonol dye as claimed in claim 1 wherein the oxonol dye is of the formula 